High chromium and vanadium in andalusite,

phengite and retrogressive margarite in contact

metamorphosed Ba-rich black slate from the
Abercrombie Beds, New South Wales, Australia
VINCENT J. MORAND*
Department of Geology and Geophysics, University of Sydney, N.S.W. 2006, Australia

Abstract
Graphitic, quartz-rich black slate within the Late Ordovician Abercrombie Beds, Lachlan Fold Belt,
southeast Australia, has undergone contact metamorphism adjacent to the Siluro-Devonian Wyangala
Batholith. This produced porphyroblasts of andalusite and cordierite, and smaller grains of pale
green phengitic mica. Later regional metamorphism caused complete retrogression of cordierite and
partial retrogression of andalusite, with margarite replacing some andalusite.
The aluminous minerals andalusite, margarite and phengite all contain V and Cr substituting for
A1. Andalusite has up to 1.39% V203 and 1.09% Cr203, margarite has up to 1.07% V203 and
0.37% Cr203, and phengitic mica has up to 6.93% V203 and 1.52% Cr203. This mica also has
BaO contents of up to 1.96%.
Chemical analyses reveal very high SiO2 contents for these rocks (about 89%), carbon contents
of about 2%, and extremely low CaO, FeO, MgO and Na20. Although V and Cr are prominent
in aluminous minerals, their concentrations in the rock are only about average for black shales.
However, Ba values range from 2000 to 6000 p.p.m., well above average for black shales. It is
suggested that V and Cr probably precipitated from sea water, but Ba may have been concentrated
by planktonic organisms such as radiolaria.
KEYWORDS: black slate, andalusite, mica, barium, vanadium.

Introduction
B LACK shales, deposited in anoxic conditions in
mainly marine environments, are known to be
enriched in a number of elements, mainly metallic, including Ba, V and Cr (Vine and Tourtelot,
1970). These elements may also be concentrated
in certain porphyroblasts when black shales are
metamorphosed. In particular, various metallic
elements may substitute for A1 in minerals such
as andalusite and potassic white mica (Deer et
al., 1982; Guidotti, 1984; Carlson and Rossman,
1988). This study looks at both aspects of a
sequence of black slates in which the aluminous
minerals andalusite and margarite have high V
and Cr, and potassic white mica is enriched in
V, Cr and Ba.
*Present address: Department of Geology, James Cook
University, Townsville, Qld 4811, Australia

Geological setting
Black, carbonaceous shale and slate is widespread in the Ordovician of the Lachlan Fold Belt
of southeastern Australia (Joplin, 1945). It commonly contains graptolites and radiolaria. The
black slate described here occurs as layers within
a sequence of metapsammite, slate, quartzite and
chert, known as the Abercrombie Beds, in eastern
New South Wales (Fig. 1). This sequence was
deposited as turbidites and pelagic sediments,
probably at the base of the continental slope
(Morand, 1984). It has been complexly deformed
and metamorphosed to greenschist facies (Motand, 1987, 1988a). Graptolites in the black slate
indicate a Late Ordovician age (Morand, 1984).
Ordovician rocks similar to the Abercrombie
Beds crop out over a large area of the Lachlan
Fold Belt (Packham, 1969). They are thought to
have been deposited in a back-arc environment
adjacent to a volcanic arc of basaltic to andesitic

Mineralogical Magazine, September 1990, Vol. 54, pp. 381-391

9 Copyright the Mineralogical Society

382

V. J. M O R A N D
o

8,00kin

EFIG.2 Y

N
FIG. 1. Location of study area in the Lachlan Fold Belt
of southeastern Australia.

character, with sediment derived from Precambrian cratonic regions to the south or west
(Powell, 1983).
The Abercrombie Beds were intruded by the
granitic Wyangala Batholith of Siluro-Devonian
age, around which a contact aureole has been
developed (Fig. 2). Intrusion was followed by
folding and regional metamorphism, causing
retrogression in the contact aureole (Morand,
1988a). Rocks in the contact aureole, which
includes some black slate, are thus polymetamorphic.

Petrography
Black slate unaffected by contact metamorphism. Black slate in the Abercrombie Beds is
carbonaceous, quartz-rich shale that has been
metamorphosed to greenschist facies. It is finegrained, commonly laminated, with layers rich in
fine detrital quartz and muscovite grains alternating with hemipelagic layers consisting of quartz,
metamorphic white mica, graphite and pyrite.
Slaty and crenulation cleavages are ubiquitous.
Chert-like layers rich in radiolarian remains (now
recrystallized quartz) are common, and many
black slate layers grade into chert.
Quartz is the most abundant mineral. Most is
recrystallized, but small detrital grains can be
recognized in many specimens, as can detrital
muscovite. Accessory detrital minerals are rutile,
tourmaline, epidote, apatite and monazite.

Miocene Basalt
Siluro - Devonian Wyangala
Batholith
Late Ordovician Abercrombie
Beds with black slate layers
Contact aureole
Fl6. 2. Geological map of the Reids Flat area, with
locations of specimens which have been analysed or
have provided mineral analyses.

Chlorite and biotite zones are present in the

Abercrombie Beds, but the metamorphic assemblage is the same in both zones, namely, quartzwhite-mica-graphite-pyrite. Chlorite is rare, and
in the biotite zone biotite is absent. This is because
these rocks are poor in iron and magnesium, and
most of the iron is taken up in pyrite and possibly
phengitic white mica.
Contact metamorphosed black slate. The petrography of these rocks has been described by Motand (1988b). The most obvious effect of contact
metamorphism is the crystallization of porphyroblasts of andalusite of the chiastotite variety
(about 0.5 to 1 mm wide and up to 8 cm long)
and ellipsoidal cordierite grains (less than 1 mm
across). Cordierite is completely retrogressed to
micaceous aggregates, but andalusite ranges from
fresh to completely altered to muscovite or mar-

H I G H - C r AND V SILICATES
garite plus muscovite. Margarite has only been
found in the westernmost layer of black slate on
Fig. 2.
Pale green potassic mica occurs as small porphyroblasts about 0.2mm long. The groundmass
is mainly recrystallized quartz with small flakes
of white mica and granules of graphite. Other
minerals observed in contact metamorphosed
black slate are pyrite, tourmaline, rutile, chlorite,
hematite, monazite and xenotime.

Conditions of metamorphism
Temperatures during contact metamorphism
were between 500 and 550~ with pressure probably about 3 kbar (Morand, 1984). A temperature
of 450 to 530~ (at 3 kbar) has been suggested
for the retrogressive metamorphism that followed
(Morand, 1988b).

Mineral chemistry
The aluminous minerals andalusite, margarite
and white mica (V-Cr mica) have been analysed.
Analyses were performed on the electron microprobes at the University of Sydney and Monash
University Department of Earth Sciences, using
wavelength-dispersive techniques. Silicate Standards were used for all elements except V, for
which metallic V was used. Analyses of andalusite
and margarite are averages of two or three spot
analyses, but most analyses of white mica are
single spot analyses because of the small size and
chemical heterogeneity of this mineral. Specimen
numbers are those of the collection at the Department of Geology and Geophysics, University of
Sydney. Tables 1, 2 and 3 have only selected
analyses. The complete set of analyses can be
obtained from the author on request.
Andalusite. In some specimens andalusite has
a pale yellow colour with the following pleochroic
scheme: c~= pale yellow,/3 = 3' = colourless. This
is an unusual colour for andalusite, which is
usually pink or green if coloured (Deer et al.,
1982) and is related to the high vanadium content
(analyses Table 1). Values of V203 reach 1.39%
and Cr203 reaches 1.09%. V and Cr replace A1,
which shows an inverse relationship with V + Cr
(Fig. 3a).
Reports of andalusite with significant V and Cr
are rare. Chinner et al. (1969) reported a maximum of 0.02% V metal for andalusite, and
Schreyer et al. (1981) reported andalusite with 2%
Cr203. The only recorded occurrence of andalusite with comparable chemistry is from a similar
rock type in Texas (Carlson and Rossman, 1988).
Andalusite from the Abercrombie Beds has neg-

383

ligible Mn and very low Fe (Table 1), so the colour

cannot be attributed to these elements. Cr imparts
a faint red colour to Cr-bearing andalusite from
Zimbabwe (Schreyer et al., 1981). Thus the yellow
colour appears to be due to V. The andalusite
reported by Carlson and Rossman (1988) has the
same pleochroic scheme as that described herein,
which they attributed to the combined effects of
V and Cr.
Those grains with the strongest yellow colour
have the highest V contents (e.g. specimen
62573). In specimen 62568 andalusite is colour
zoned from colourless in the centre to yellow at
the edges. Seven spots across one grain were analysed for Cr203 and V203 (Fig. 4). There is an
increase in both Cr203 and V203 from the centre
to the edges, but since Cr content is quite low,
the yellow colour appears to be due to V. Only
those andalusite grains with V203 greater than
about 0.8% display a yellow colour.
Margarite. The chemistry of this mineral has
been dealt with by Morand (1988b). In summary,
margarite has significant replacement of Ca by
Na, and has relatively high V and Cr, with up
to 1.07% g203 and 0.37% Cr203 (Table 2).V and
Cr substitute for A1vi (Fig. 3b).
V - C r mica. This is a phengitic mica with high
V and Cr. Grains of this mica are not homogeneous, but are either interlayered with colourless white mica (closer to muscovite in
composition) with a sharp boundary between the
two phases, or else there is a continuous variation
in V and Cr contents across the layers. It has a
higher relief and birefringence than muscovite,
and the pleochroism is: c~=pale blue-green, /3
= , / = p a l e green. These colours are midway
between those of the Cr-mica fuchsite and the
V-mica roscoelite (Deer et al., 1962).
Analyses (Table 3) show that both the absolute
and relative amounts of Cr and V in this mica
vary for different rock specimens, with Cr203 up
to 1.52% (62569) and V203 up to 6.93% (62568).
However, the ratio of V/(V+Cr) is similar for
all parts of the one grain. As in margarite, V and
Cr are assumed to be in the trivalent state,
although mica with similar composition from a
similar rock type reported by Snetsinger (1966)
has both V 3+ and V 4+.
Fig. 3c shows A1vi plotted against V + Cr for
V-Cr mica, and also colourless potassic mica
pseudomorphing andalusite. The latter mica also
contains some V and Cr. It is probably not in
equilibrium with the V-Cr mica as it post-dates
contact metamorphism. An inverse relationship
exists between A1w and V+Cr, indicating substitution of V + C r for octahedral A1. The amount
of V + C r in mica pseudomorphing andalusite is

384

V. J. M O R A N D

8.00

50

7.95

4.05

0~176 9 9
~

7.90

<i:

4.10

O0

>

,<

OO0

7.85

4.00

8o

3.95

oo

7.80

3.90

9
,I

7.75
0.00

I
0.05

3.85

i
I
0.10 0.15

0.05

V+Cr

4.0-

0.15

Oo

3.8-

1;~oO~

3.6-

~ ',,o ~ ,~

2.8]32
0

0.10

V+Cr

4.0 ~L~

,.~ 3"6t

~"

0.00

' 022 ' OJ4

3.43.2

", :" ." : ..

3.02.8

0'.6 ' 0'.8 '

2.60.0

V+Cr

o o'.'--

go

'

O.()4'

'
0.08

'

O.12'

'
0.16

Ti

FIG. 3. (a) Cation values of A1 plotted against V + Cr for andalusite. (b) Cation values of A I vi against V + Cr
for margarite. (c) Cation values of A1 vi against V + Cr for potassic micas. Open circles are micas pseudomorphing
andalusite, closed circles are V-Cr micas. (d) Cation values of A1vi against Ti for potassic micas. Symbols as
in (c).

less than 0.15 atoms per formula unit, which is

comparable to V + C r contents in both andalusite
and margarite. In the V-Cr mica, V+ Cr can reach
about 0.9 atoms per formula unit.
Both V-Cr mica and pseudomorphous mica are
phengitic, with significant Mg and Fe contents and
Si slightly high because of the celadonite substitution (Fe 2 + ,Mg 2 + )Si4 + =A1 3 + A13 + . Titanium is
also present, some grains having well over one
weight percent TiO2. Fig. 3d shows that Ti substi-

tutes for A1vi and that V-Cr mica and pseudomorphous mica form two distinct groups with a boundary at 0.03 atoms Ti. The coupled substitution
Ti 4 + A13 + =A1 3 + Si4 + lowers the Si content and
tends to offset the increase in Si due to the celadonite substitution.
Some micas from two rock specimens (62582
and 62568) were analysed for Ba (Table 3).There
is significant Ba in both types of mica, but V-Cr
mica has much less BaO (0.33 wt.%) than mica

H I G H - C r AND V S I L I C A T E S
TABLE t

385

ANDALUSffE ANALYSES FROM CONTACT METAMORPHOSED BLACK SLATE, REIDS FLAT AREA, N.S.W.
62568
AND 1

62568
AND 6

62568
AND 10

62569 82589
AND 1 AND 5

62569
AND 7

82573
AND 1

62573
AND 2

62611
AND 1

62611
AND 4

SiO2

37.10

36,85

TiO2

0,07

0.06

36.79

36.87

36.87

38.76

37.37

37,58

36.59

37.25

0,10

0,09

0.10

0.13

0.07

0.04

0.13

61.49

0.04

62.39

61,34

62.18

62,49

62,82

61.59

61.35

60,07

60.57

V203
Cr203
Fe203"

1.12

0,66

1.39

0.40

0.30

0.26

9,23

0.26

0,83

1.04

0.07
0.06

0.10
0.01

0.15
0.03

0.09
0.09

0.11
0,04

0.05
0.03

0.44
0.07

0.39
0.12

1.09
0.07

0,75
0.07

MnO
MgO

0.00
0.05

O,0O
0.07

0.01
~

0,00
0.06

0.00
0.07

0.00
0.04

0.00
~

0.03
0.02

0.00

0.09

Total

99.98

100,14

99,89

99.78

89.97

100.12

99,81

99.77

99.52

99.75

AI203

No.

of catlonsl2O(O)

Si

4,019

3.980

3,994

3,997

3,985

3.968

4.047

4.071

3.994

4.081

A]

7.853

7,944

7.850

7.944

7,963

7,991

7.863

7.831

7.818

7.768

T[

0.006

0.005

0.008

0.006

0.009

0.011

0.006

0.003

0.011

0.003

0.098

0,057

0.121

0.035

0,025

0.023

0.019

0.023

0.072

0.090

Or

0.007

0.009

0.013

0.008

O.00g

0,004

0.038

0.034

0.094

0.064

Fe 3+

0.005

0.001

0.003

0.006

0.004

0.003

0,005

0.009

0.005

0.008

Mg

0.008

0.010

0,014

0.007

0.010

0.011

0.007

0.005

0.003

0.005

Mn

0.000

0,000

0.001

0.000

0.00O

0.00O

0.000

0.003

0.000

Total

12.00

12,01

12.00

12.06

12.01

12.01

11.99

11.98

11.90

11.98

0.86

0,g0

0.81

0.74

0.85

0.33

0.40

0.43

0,53

V/(V + Cr) 0.93

*All iron treated as Fe3+

replacing andalusite (up to about 2%). Micas in

other specimens probably also have Ba substituting for K, which may account for the low X totals.
Na is present in both mica types, usually in
amounts of about 0.5% Na20.
In summary, the micas show substitutions in
the interlayer sites and coupled substitutions in
the octahedral and tetrahedral sites. Interlayer
cations have paragonite (Na) and oellacherite
(Ba) substitution for muscovite, and the octahedral cations show phengite (Mg,Fe), roscoelit e (V)
and fuchsite (Cr) substitutions, as well as TiVlApV
substitution. Micas replacing andalusite are closer
to pure muscovite in composition.

Geochemistry of black slate

Six specimens of black slate were analysed by
X-ray fluorescence at the Department of Geology
and Geophysics, University of Sydney, for major
elements and selected minor elements (Table 4).
Four of the rocks are from within the contact aureole and two (62625 and 62651) come from outside the contact zone (Fig. 2). Analyses were
carried out on approximately 100gin samples of
clean rock chips. They were ground in a Tema
tungsten carbide vessel for 90 seconds. Major
element analyses were performed on fused discs.
Trace elements (Mn, Cr, Ce, Nd, Sin, Ba, La

and V) were analysed on pressed powder pellets.

Both sets of analyses were done on a Philips
PW1450 X-ray spectrometer. Iron was oxidized
to Fe203 and results were corrected for loss on
ignition. Four specimens (62568, 62634, 62611,
62625) were analysed for HzO and carbon. Carbon was analysed by LECO induction furnace
combustion method, followed by gravimetric
finish (Nesbitt bulb absorption tubes filled with
Ascorite CO2 absorbent). Water was analysed
using the rapid water method with LECO induction furnace, followed by gravimetric finish.
With the exception of 62611, carbon plus water
values are very similar to loss on ignition values,
and it is assumed that L.O.I. in 62582 and 62651
is also composed almost entirely of water and carbon. A small amount of sulphur must be present
since the rocks contain pyrite, and this, along with
possible CI and F, would constitute a small fraction of L.O.I. Carbon is assumed to be elemental
C (graphite) and no CO2 was indicated by qualitative tests. Iron contents are so low that oxidation
to Fe203 makes a negligible contribution to
L.O.I. Totals in Table 4 are low because of the
high content of trace elements, especially Ba.
All the analyses have extremely high SiO2, and
thus other major elements are correspondingly
low. The only oxides constituting more than 1%
are SiO;, A1203 and K20. Despite the extreme

V. J. M O R A N D

386

ZONE OF
INCLUSIONS
" ~ ANDALUSITE

~2L

--5;~[j
e vd A A

~
~_~
1

mii

%//

~.,~..'.4 6

MUSCOVITE ALTERATION

0.3mm

1 2

4567

Cr20 3 %
V20 3 %
1"0]

o18

1.00 4

0.95

0.90 -

0.85 -I'--~"
0.80 /

v+Cr

.
~

FIG. 4. Drawing of a zoned andalusite grain, with values

of V203 and Cr203 for each analysed point, and ratio
of V/(V + Cr) in cations. The centre of the grain is colourless, the margins are yellow.

blackness of some analysed samples, carbon contents are only about 2%.
Specimen 62625, from outside the contact aureole, differs from contact metamorphosed specimens in having lower SiO2 and C, and higher
TiO2, A1203, MgO, Na20, K20 and H20. Unlike
the other samples analysed, this specimen has a
well developed crenulation cleavage, the formation of which involves significant solution transfer
of material along the cleavage seams (Gray,
1979). Thus most of the chemical differences in
specimen 62625 can be ascribed to preferential
dissolution and removal of quartz, with concomitant concentration of mica and therefore A1203,
K20, Na20, H20 and MgO (assuming a phengitic
composition). Silica appears to have been rede
posited in the abundant quartz veins that occur

in outcrops of black slate. The low C content is

difficult to rationalize, as graphite should be concentrated in cleavage seams along with mica. It
may simply be a primary feature of the rock.
The other specimen from outside the contact
aureole (62651) has major element contents similar to those of the contact metamorphosed rocks,
except that FeO and MgO are higher in this specimen. This raises the possibility of metasomatism
during granite intrusion, but the data are too few
to give a clear picture. Metasomatism is considered unlikely, as pelites do not normally
undergo metasomatism during contact metamorphism.
Trace element contents of the contact metamorphosed rocks are quite variable, particularly
Ba, V and Cr. The two specimens from outside
the aureole have trace element contents within
the range shown by those within the aureole,
except that V in 62625 is low. As the V content
in the other specimen from outside the contact
aureole is relatively high, no significance in terms
of metasomatism during intrusion can be attached
to this value. Ba in 62625 is high, but within the
range shown by contact metamorphosed rocks.
Thus, black slate from the contact aureole and
from outside it show non-systematic variations in
some major and trace elements, but the data do
not support metasomatism due to granite
intrusion.
Some of the few analyses of black slates from
the Lachlan Fold Belt available for comparison
with the data presented here are those of Joplin
(1945). Compared with black slate from the Abercrombie Beds, her analyses, which are from various Late Ordovician localities in New South
Wales, have less SiO 2 and more A1203 and K20 ,
but all have similar AlzO3/K20 ratios of about
5. Thus black slate from the Abercrombie Beds
had lower initial clay contents than those from
elsewhere in the Lachlan Fold Belt, but the clay
was probably the same composition in all of them.
Analyses from Table 4 and from Joplin (1945)
are shown on an A ' K F diagram (Winkler, 1979)
in Fig. 5. They mostly lie in the field andalusitecordierite-muscovite. On Fig. 5, the analyses
from the Abercrombie Beds lie within the range
of compositions of Joplin (1945), and are thus
considered to be typical of Ordovician black slate
in New South Wales.
Although 62568 contains margarite, a calciumbearing mica, it has less than measurable CaO
(Table 4). However, the small amount of margarite present ( < 1 % modal) would account for no
more than 0.05% of CaO. All samples have CaO
at or below the detection limit.
Of the trace elements determined, Ba is the

HIGH-Cr AND V SILICATES

TABLE 2

387

MARGARITEANALYSESFROMBLACKSLATE.REIDSFLATDISTRICT,N.S.W.

K20
Total

62568
M~
31.40
0.04
49,36
0,90
0,02
0.21
0.01
0,64
10.57
1.73
0.o2
94.90

62566 62568 62566

M~cG5 Ma,FG7 ~
30,73 31.72 31.10
0.06
0.08
0.04
49.85 48.96 49.52
0,93
0.69
1.07
0.09
0,06
0.06
0.15
0,14
0.16
0.70
0.70
0.76
11.52 10.66 10.33
1.62
1.73
1.47
o02
~
~
95,67 9 5 . t l
94.54

Si
AIiV
AIvi
Ti
V
Cr
Fe
Mn
Mg
Ca
Na
K

4,170
3.824
3,016
0.004
0.096
0.002
0.023
0.001
0.127
1,507
0.446
0,003

4.074
3.926
3,861
0.006
0.098
0.009
0.017
0.138
1,635
0.416
0.003

4,216
3.784
3.885
0.009
0.073
0.007
0.015
0,140
1.518
0.446
0.063

4.147 4 . 1 0 3 4 . 1 3 8
3.853 3.807 3.062
3,933 3.909 3,993
0.004 0.005 0.006
0.115 0.030 0.020
0.007 0.007 0.000
0,018 0.019 0.013
0.007 0.151 0 . 0 9 4 0 . 0 8 8
1.476 1 . 5 4 7 1 . 6 3 0
0.382 0.346 0.298
0,005 0.003 0,005

1.96
4.17

2.05
4.13

2.03
4.13

1.86
4.23

1.89
4.17

V/(V+Cr)
0.98
0.92
*All iron treated as Fe2+

0.91

0.94

0.85

SiO2
TiO2
AI203
V203
Cr203
FeO*
MnO
MgO
CaO

62569
MAR~'
31.77
0.05
50.18
0.36
0.07
0.17
0.06
0.48
10.87
1.38
~
95.38

62569 62569
~p~G5 P,r
31.19 30,46
0.05 0.07
50.31 50,76
0,19 0,43
0.05 0.05
0.11
0.16
0.44 0,60
11.46 10.72
1,16
1.49
0o3
0.03
94,99 94.77

62569
~
30.78
0.05
50,16
0.15
0,37
0.20
0.02
0.42
11.09
1.73
o02
94.99

62569
~
30.46
0.05
50.63
0.20

4.055
3.945
4,017
0.007
0.046
0.005
0.018
0.117
1.530
0.385
0.006

4.097
3.903
3,964
0.005
0.016
0.040
0.022
0.003
0.083
1.580
0.447
0,003

4.064
3.936
4,028
0.005
0.023
0.029
0.034
*
0.103
1.502
0.359
0.008

4.076
3.925
3.990
0.008
0.017
0.032
0.028
0,099
1,573
0.280
0.004

1.93
4.13

1.92
4.20

2.03
4.13

1.89
4.22

1.86
4.17

0.77

0.90

0.29

0.44

0.35

0.28
0.32

62689
k&e3~lO
30.69
0.07
50.57
0.16
0.31
0,26
i

0.52
10,64
1.39
o.os
04.54

0,50
11.06
1.43
o~o4
95,09

NO, o1 cations /22(0)

X
Y

TABLE 3:

ANALYSES OF POTASSIC WHITE MICA FROM BLACK SLATE

62568
62568
82568
62569
62569
62569
6 2 5 9 9 0 2 5 9 9 6 2 5 8 2 62582
62611
62611
MUSCI-1 MUSC1-3 MUSC4-2 MUSC1 MUSC2-4 MU~C4 MUSCI-1 MUSC2 MUSC2-2 MUSC3-2 MU;~K~2-1. MU~C3-1

SiO2
TiC)2
AI203
Cr203
V203
FeO*
M~O
MgO
CaO
Na2O
K20
BaO

45.76
1.41
29.53
0.44
6.08
0.24
0.02
1.18
0,40
9,95

0,39
10,00

Total

95.01

95.23

0.00

45.97
1.27
28.59
0.51
6.93
0.24
0.06
1,26
0.00

45.32
0.18
35.67
0.13
1.20
0.13
0.61

0.34
9.27

46.54
0.13
37.78
0.07
0,40
0.19
0.CO
0.42
0.01
0.61
9,33

46.13
1.15
33.02
0.03
2.50
0.37
0,01
1.32
0.00
0.45
10.15

45.73
0.92
31.35
0.29
4.18
0.54
0.01
1.18
0.01
0.27
10.40

46.90
1.16
31.00
0.14
3,48
0.35
1.14
0.35
0.67
0.33

46.31
0.31
34.38
0.37
0.62
0.32
1,15
0.39
9,84
1,69

94.0~

95.48

95.13

94.88

94.73

95,38

95,24

95.61

95.45

6.168
1.832
3.422
0.085
0.043
0.226
0.066
0.235
0.000
0.000
0.104
1.712

6.218
1.782
3.390
0.086
0.032
0.269
0.053
0,239
0.002
0.000
0.100
1.671

6.012
1.988
3.572
0.018
0.042
0.022
O.140
0.392
0.006
0,0(~
0.140
1,787

1.82
4.08
0.84

1.77
4.07
0.89

1.93
4.19
0.34

44.44
1.39
30.88
1.52
6.50
0.64
0.00
1,13

45.41
1.20
30.27
1.07
4.66
0.43
0.04
1.33

0.00

0.00

0,49
9,25
1.96

0,27
8,39

94.94

95.16

46.24
0.85
33.41
0.41
2.11
0,59
0.00
1.18
0.00
0.40
10.06

46,87
0.86
33.07
0.31
2.53
0.48
0.02
1.21
0.00
0.39
9.87

62673
MUSC1

_ _

45.08
0.18
35.32
0.40
0.21
1.25
0.05
1,97
0.01
0.54
10.49
m

No. o f I o n s / 2 2 ( 8 )
Si
A~v
AFt
"13
Cr
V
Fe
Mg
Mn
Ca
Na
K
Ba

6.198
1.802
2.914
0.143
0.047
0.661
0.027
0.239
0.002
0.000
0.016
1.71g

6.233
1.767
2.804
0.130
0.055
0.753
0.027
0.255
0.007
0.000
0.103

6.089
1.911
3.738
0.019
0,015
0.129
0.015
0.122

1.713

0.128
1.585
0.103

X
Y
V/(V+Cr)

1.74
4.03
0.93

1.83
4.03
0.g~

1.82
4.04
0.90

5.999
2.001
2.913
0.141
0.162
0.704
0.072
0,227
0,000
0.000
0.069
1.445

6.181
1.819
3.038
0.123
0.115
0.509
0.049
0.270
0.005
0.000
0.116
1.729

6.096
1.904
3.928
0.013
0.007
0.042
0.021
0.082
0,000
0.002
0.153
1.559

6.167
1.833
3.368
0.116
0,003
0.268
0.041
0.263
0.001
0.000
0.116
1.729

6.181
1.819
3.176
0.093
0.031
0.453
0.061
0,238
0.001
0.002
0.071
1.793

6.308
1.692
3.224
0.117
0.015
0.377
0.040
0.229

6.200
1.800
3.623
0.031
0.040
0~066
0.036
0.230

0.144
1.660
0,017

0.100
1.680
0.089

1.51
4.22
0.81

1.70
4.11
0.82

1,71
4.09
0.87

1.85
4.06
0.99

1.87
4.05
0.94

1.82
4.00
0.95

1.87
4.03
0.62

"All iron treatedas Fe 2+

62568 MUSC4-2, 62569 MUSC4, 62582 MUSC3-2 and 62673 MUSC 1 ere rNcas pseudomorphlng~'ldalustte;otheranalysu are Of V-Cr mica.

388

V. J. MORAND
TABLE 4

WHOLE ROCK ANALYSES OF BLACK SLATE FROM THE ABERCROMBIE BEDS

62568

62582

62634

62611

62625

62651

SiO2

87,99

88.43

89.08

89.48

84.92

89.67

TiO2

0.23

0.26

0.20

0.18

0.39

0,18

AI203

5.83

5.49

5.16

4.08

7.77

5.32

FeO*

0.17

0.13

0.18

0.32

0.29

0.46

M~

0.21

0.20

0.21

0,23

0,69

0.40

<0.05

0.06

<0,05

<0.05

<0,05

<0.05
<0.10

Na20

0.36

<0.10

0.24

<0.10

0.54

K20

1.26

1,36

1.43

0,86

1.97

1.25

P205

<0.05

<0.05

<0.05

<0.05

<0.05

<0.05

H20 +

0.62

0.60

0.57

1.20

H20-

0,12

<0.01

0.21

0.07

2.35

2.27

1.14

Total

C'*

99.42

2.41
95.93

99.45

98.20

98.98

97.28

L.O.I.

3.35

3.06

2.98

3.41

2.57

1.88

Trace Elements In p.p.m.

Mn

<20

154

23

22

35

23

Ba

2210

1670

2060

6260

5540

2550
663

785

582

609

212

97

Cr

62

85

126

89

82

77

La

17

21

18

45

22

15

(39

29

34

23

47

46

40

Nd

15

20

13

24

12

16

Sm

<3

<3

<3

<3

All iron treated as FeO. Separate FeO and Fe203 values not determined.
* *

All carbon treated as elemental carbon,

L.O.I.

= loss on ignition.

Ar

K K fels

Blot

FIG. 5. A'KF diagram with black slate compositions

from the Reids Flat area (dots) and from Joplin (1945)
for various localities in New South Wales (crosses).
Mineral assemblages shown are those of medium grade
contact metamorphism (Winkler, 1979).

No CO2 was detected.

most abundant, ranging up to more than 6000

p.p.m, or about 0.7% BaO. The only mineral in
these rocks that can accommodate a large cation
such as Ba is potassic mica. Micas in two specimens, 62582 and 62568, have significant Ba substitution in the interlayer sites (Table 3). No distinct
Ba phase, such as baryte, has been observed.
In order to determine if these black slates have
unusual chemistry, given their distinctive mineral
compositions, it is instructive to compare them
to 'average' black shale or slate. The only comprehensive data set on black shale compositions is
that of Vine and Tourtelot (1970), who studied
the geochemistry of black shales from the U.S.A.
and Canada, with major and trace elements determined for 20 sets of black shales. These sets were
drawn from various ages and environments. Of
the 12 elements A1, Fe, Mg, Mn, Ca, Na, K, Ti,
Ba, Cr, V and La, only Ba and V average values
from this study are in quantities greater than the
average for American black shales (Table 5). The
major elements A1, Fe, Mg, Mn, Ca, Na and K
are present in significantly lower concentrations
than in the American shales. Although several
minerals in the black slate from the Abercrombie

H I G H - C r AND V S I L I C A T E S
TABLE 5

AVERAGEELEMENTALABUNDANCES IN PERCENT OF BLACK SHALES

.t~veraqe Attlerical Black S]3ale*

Ave~aoe from this Studv

AI

7.0

3.0

Fe

2.0

0.2

Mg

0.7

0.2

Ca

1.5

<0,04

Na

0,7

0.14

2.0

1.1

Ti

0.2

0.17

Mn

0.015

0.004

Ba

0.03

0.34

Cr

0.01

0.01

La

0.003

0.002

0.015

0.05

From Vine & Tourtelol (1970).

389

equivalents from other parts of the world also

have significant V and Cr, as is the case for the
occurrence described by Carlson and Rossman
(1988).
When mineral analyses are compared with the
whole-rock compositions, it appears that the relative amounts of V and Cr in the various minerals
are determined largely by their relative amounts
in the rock. The ratio V/(V+Cr) is similar in most
mineral analyses for each specimen (Fig. 6), and
for the whole-rock specimens which were analysed (62568, 62582, 62611) this ratio is similar
for the whole rock and mineral analyses, although
in 62611 the mica is more V-rich than the andalusite.
Discussion

TABLE 6
MINIMUM ENRICHMENT VALUE FOR ELEMENTS IN BLACK SHALES FROM
VINE & TOURTELOT (1970), COMPARED TO THIS STUDY. VALUES IN
PERCENT.
American Black Shale

Maximum Value from this Study

Ti

0.7

Mn

0.1

0.27
0.02

Ba

0.1

0.63

Cr

0.07

0.01

La

0.007

0.005

0.1

0.08

Beds have significant V and Cr, whole-rock Cr

is equal to the average value for American black
shale and V is not greatly higher than the American average.
Of the averages of trace elements for the black
slates, only Ba has a value greater than Vine and
Tourtelot's minimum enrichment value, that is,
the amount of an element above which the rock
is considered to be enriched in that element
(Table 6). When the individual analyses of Table
4 are considered, no samples have any elements
in abundances exceeding their minimum enrichment value except Ba, which is above this value
in all samples.
Thus black slate from the Abercrombie Beds
is not enriched in any metallic element except Ba,
and has significantly different major element
chemistry compared to average American black
shale. Although minerals such as andalusite and
mica have unusually high V and Cr contents in
these rocks, the whole-rock V and Cr are not
much higher than average. It is therefore likely
that minerals in black slate or its higher grade

Provenance of the black slate. The high SiO2

content and fine grain-size of Ordovician black
shales in the Lachlan Fold Belt led Joplin (1945)
to postulate that they were derived from silicic
volcanic activity. However, silicic volcanics are
virtually absent from the Ordovician of the Lachlan Fold Belt (Cas, 1983). The absence in these
rocks of detrital feldspar or altered relics thereof
also mitigates against such an origin.
Features such as the high quartz content and
detrital minerals such as muscovite, tourmaline,
rutile, monazite, apatite, epidote and xenotime,
indicate that these rocks are derived from source
rocks similar to those of the quartz-rich turbidites
of the Abercrombie Beds, namely, Precambrian
or Cambrian rocks from the nearby Gondwana
craton (Powell, 1983). Silica precipitated from sea
water also contributed to the high quartz contents,
especially in the more chert-like layers. The black
slates were deposited as the finest fraction carried
by turbidity currents or bottom currents, mixed
with pelagic material such as organic remains and
very fine quartz detritus which settled out of the
water column.
Origin of vanadium, chromium and barium. In
the rocks of this study, the analysed trace
elements which occur in greatest quantity are Ba,
V and Cr. Holland (1979) and Berry et al. (1986)
found that metal enrichment in organic-rich sediments can probably be achieved by chemical precipitation from sea water and reactions with dead
organic remains. As V and Cr are not present
in excessive amounts in the Abercrombie Beds,
there is no need to invoke concentration by
organisms (cf. Goldberg, 1957).
Ba in these rocks is in much higher concentrations than average, and is also much more
abundant than any other trace element analysed.
BaO is generally higher than TiO2, FeO, CaO,

390

V. J. M O R A N D

No.

62568

No.

62582

2,-~, M,ca

~ j

0.60 0.70 0.80 ~

0

v
i v+Cr

1.00

No.

62573

No.

62599

2 -~ ~
Mica
0 i i J t i i

2
6~And.

!
v

g
I

.
[

~And.
o

v
f

V+Cr

0.90 1.00
1

___K__
v
V+Cr

, , ,
oo,oo,o

No.

62569
ica

4
]

0.80

[ if

,~ 1.00

2
0

21

0 t

62611

NO.

0
t

0 I r
0.40

0.60

l
i

0.80

V+Cr

1.00

V+er

0.60 0.70 0.80 0.90

FI6. 6. V/(V + Cr) ratios plotted against number of analyses for mica, margarite and andalusite in six specimens
of black slate, and whole rock value (indicated by arrow) for specimens 62568, 62611 and 62582.

Na20 and P205, and is about equal to MgO in

concentration (Table 4).
Organic activity may be responsible for concentrating Ba in these rocks. Certain organisms in
the Black Sea are known to concentrate Ba (Vinogradova and Koval'skiy, 1962), including zooplankton whose ash contains up to 2000p.p.m.
Ba, and some phytoplankton which can have up
to 30,000 p.p.m. Ba. Ordovician black slate in
the Abercrombie Beds contains radiolarian
remains, and it is possible that these planktonic
organisms were able to concentrate Ba and hence
lead to high Ba values in the black shale.
Conclusions

Late Ordovician black slate in the Abercrombie

Beds, Lachlan Fold Belt, New South Wales, was
derived from hemipelagic sediments deposited

within a turbidite sequence. Detrital material in

the black slate suggests the same provenance as
the turbidites, namely the Gondwana craton to
the south or west.
Contact metamorphism against the Siluro-Devonian Wyangala Batholith produced andalusite,
cordierite and a phengitic mica containing V and
Cr. Margarite replaces andalusite in some rocks.
It grew during retrogressive regional metamorphism. Both andalusite and margarite contain V
and Cr. In all these aluminous minerals V and
Cr substitute for AI, with the ratio of V to Cr
similar for all minerals in the one rock. Ba is present in the phengitic mica.
The rocks have very high silica (about 89%)
and high Ba (2000 to 6000 p.p.m.). V and Cr occur
in about average amounts for black shale, whereas
all other major elements, and those trace
elements determined, are well below average. V

HIGH-Cr AND V SILICATES

and Cr were probably precipitated from sea
water, but Ba may have been concentrated by
planktonic organisms such as radiolaria.

Acknowledgements
This work was part of a Ph.D. project at the University
of Sydney which was funded by a Commonwealth Postgraduate Research Award. Diana Benson and Alf Hohmann assisted with electron microprobe analyses. Roll
Beck greatly assisted in the whole-rock analysis. Mike
Rubenach provided critical discussion of the manuscript.

References
Berry, W. B. N., Wilde, P., Quinby-Hunt, M. S. and
Orth, C. J. (1986) Norsk Geol. Tidds. 66, 45-51.
Carlson, W. D. and Rossman, G. R. (1988) Am.
Mineral. 73, 1366-9.
Cas, R. A. F. (1983)A review o f the palaeogeographic
and tectonic development of the Palaeozoic Lachlan
Fold Belt o f south eastern Australia. Geol. Soc. Austral. Spec. Publ. No. 10.
Chinner, G. A., Smith, J. V. and Knowles, C. R. (1969)
Am. J. Sci. 267A, 96-113.
Deer, W. A., Howie, R. A. and Zussman, J. (1962)
Rock-forming Minerals', Vol. 3, Sheet Silicates, John
Wiley, New York.

391

- - (1982) Rock-]orming Minerals, Vol. 1A,

Orthosilicates. 2nd ed. Longman, London.
Goldberg, E. D. (1957) In Ecology (Hedgpeth, J. W.,
ed.) Geol. Soc. Am. Mem. 67, 1: 345-57.
Gray, D. R. (1979) Am. J. Sci. 279, 97-128.
Guidotti, C. V. (1984) In Micas. Reviews in Mineralogy,
Vol. 13 (Bailey, S. W., ed.) Mineral. Soc. Am.,
357-467.
Holland, H. D. (1979) Econ. Geol. 74, 1676--80.
Joplin, G. A. (1945) Proc. Linn. Soc. N.S.W. 70,
158-72.
Morand, V. J. (1984) Ph.D. thesis, University of Sydney.
- - (1987) Austral. J. Earth Sci. 34, 119-33.
--(1988a) Ibid. 35, 339-53.
- - (1988b) Mineral. Mag. 52,341-5.
Packham, G. H. (1969) In Geology of New South Wales
(Packham, G. H., ed.) J. Geol. Soc. Austral. 16,
76-103.
Powell, C. McA. (1983) Ibid. 30, 353-74.
Sehreyer, W., Werding, G. and Abraham, K. (1981)
J. Petrol. 22, 191-231.
Snetsinger, K. G. (1966) Am. Mineral. 51, 1623-39.
Vine, J. D. and Tourtelot, E. B. (1970) Econ. Geol.
65, 253-72.
Vinogradova, Z. A. and Koval'skiy, V. V. (1962) Dokl.
Acad. Nauk S.S.S.R. 147, 1458.
Winkler, H. G. F. (1979) Petrogenesis of Metamorphic
Rocks, 5th ed. Springer-Verlag, New York.
[Manuscript received 17 July 1989; revised 5 November
1989]